Electrocatalysis of Oxygen Using Water Soluble Metal Porphyrins and Chemically Modified Porphyrin Electrodes.

Abstract

Primary effort was devoted to the study of oxygen reduction using wateroluble iron and cobalt porphyrins, namely, iron and cobalt tetrakis (N-methyl-4-pyridyl)porphyrin. These porphyrins with the metal in the +3 oxidation state can be electrochemically reduced to the divalent state which can then reacted with oxygen. In the case of the iron containing porphyrin, oxygen was reduced at a bimolecular rate of ca. 1 x 10 to the minus 7th power 1/m/s to hydrogen perioxide which was then reduced rapidly to water. A mechanistic scheme was postulated for the reduction and using experimentally determined parameters, current-potential curves were simulated. Good agreement between the experimental and computer calculated current-potential curves supported the proposed scheme. Cross-correlation between optical, electrochemical and magnetic circular dichroism results have provided axial ligation, dimerization and spin state information of the ferric and ferrous tetrakis (n-methyl-4-pyridyl)porphyrins. Glassy or graphitic carbon electrodes were rendered catalytic by the incorporation of iron porphyrin derivatives infinity e.g. iron tetra-(o-amino-phenyl)porphyrin and iron tetra-(N(2-hydroxyethyl)pyridyl)porphyrin summation in thin polymeric films adhering to the carbon. The extent of oxygen reduction to hydrogen peroxide and water depended on the amount of iron porphyin.

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Document Details

Document Type
Technical Report
Publication Date
Nov 01, 1983
Accession Number
ADA136062

Entities

People

  • T. Kuwana

Organizations

  • Ohio State University

Tags

Communities of Interest

  • Advanced Electronics
  • Energy and Power Technologies

DTIC Thesaurus Topics

  • Air Force
  • Catalysis
  • Chemical Synthesis
  • Chemistry
  • Electrodeposition
  • Electrodes
  • Electron Microscopy
  • Electron Transfer
  • Films
  • Materials Processing
  • Materials Science
  • Optical Analysis
  • Particles
  • Polymeric Films
  • Radio Frequency
  • Rocket Oxidizers
  • X Rays

Fields of Study

  • Chemistry

Readers

  • Electrochemical Engineering/ Fuel Cell Technologies
  • Organic Chemistry